Fungicidal compositions

ABSTRACT

Fungicidal compositions are described, consisting of mixtures comprising salts of an alkaline or alkaline-earth metal, Mn or Zn of phosphorous acid and at least a second component selected from compounds having an antifungal activity. The component having an antifungal activity can be selected, for example, from IR5885, IR6141, copper (1) or copper (11) salts (such as copper oxychloride, copper hydroxide, tribasic copper sulfate), dithiocarbamates (such as mancozeb, zineb, propineb), folpet.

The present invention relates to fungicidal compositions.

In particular, the present invention relates to new compositions capableof controlling phytopathogen agents which cause considerable economicaldamage to agricultural crops.

More specifically, the present invention relates to the use ofcompositions based on a salt of alkaline or alkaline-earth metal, Mn orZn of phosphorous acid, also called phosphites or phosphonates, in amixture with at least another component having an antifungal activity.

The Applicant has surprisingly found that the compositions based onsalts of phosphorous acid, object of the present invention, havesurprising fungicidal activities and prove to be capable of controllingnumerous diseases which can damage crops of considerable economicalinterest, such as, for example, vines, potatoes and tobacco.

With respect to analogous mixtures obtained with Fosetyl, an aluminumphosphonate having the same action mechanism, salts of phosphorous acidhave surprisingly proved to have a higher synergic effect with the othercomponents, at the same time having the advantage of a better profilefrom a toxicological and environmental point of view, as well as theadvantage of a wider range of uses. The compositions, object of thepresent invention, unlike the analogous mixtures with Fosetyl, are, forexample, capable of efficaciously controlling potato downy mildew,showing a high synergic effect.

The object of the present invention therefore relates to fungicidalcompositions consisting of mixtures comprising A) at least one salt ofan alkaline or alkaline-earth metal, Mn or Zn of phosphorous acid and B)at least a second fungicidal component. In particular, the fungicidalcomponent B) can be selected from:

-   -   1) Cymoxanil, corresponding to 1-(2-cyano-2-methoxy        imino-acetyl)-3-ethyl urea;    -   2) IR5885, a dipeptic compound corresponding to        diastereoisomeric mixtures of methyl        (S-(R,S)]-[3-(N-isopropoxycarbonylvalinyl)amino[-3-(4-chlorophenyl)propanoate        in any proportion, or to one of the two diastereoisomeric forms        S—R or S—S, considered singly;    -   3) Benalaxyl, corresponding to methyl N-(phenyl        acetyl)-N-2,6-xylyl-RS-alaninate;    -   4) IR 6141, corresponding to methyl N-(phenyl acetyl)-N-2,        6-xylyl-R-alaninate;    -   5) Metalaxyl, corresponding to methyl N-(2-methoxy        acetyl)-N-2,6-xylyl-RS-alaninate;    -   6) Mefenoxam, corresponding to methyl N-(2-methoxy        acetyl)-N-2,6-xylyl-R-alaninate;    -   7) Oxadixyl, corresponding to        2-methoxy-N-(2-oxo-1,3-oxazolidin-3-yl)aceto-2′,6′-xylidide;    -   8) Ofurace, corresponding to        DL-3-[N-chloroacetyl-N-(2,6-xylyl)-amino]-γ-butyrolactone;    -   9) Iprovalicarb, corresponding to        O-(1-methyl-ethyl)-N-[2-methyl-1-[[[1-(4-methylphenyl)-ethyl]amino]carbonyl]propyl]carbamate,        or Benthiavalicarb-isopropyl corresponding to        O-isopropyl[(S)-1-{[(1R)-1-(6-fluoro-1,3-benzo-thiazol-2-yl)ethyl]carbamoyl-2-methylpropyl]-carbamate;    -   10) Azoxystrobin, corresponding to methyl        (E)-2-[2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]phenyl-3-methoxyacrylate;    -   11) Kresoxim-methyl corresponding to methyl        (E)-methoxyimino-α-[(o-tolyloxy)-o-tolyl]-acetate;    -   12) Metominofen, corresponding to        N-methyl-(E)-methoxyimino-(2-phenoxyphenyl)acetamide;    -   13) Acibenzolar, corresponding to methyl        benzo-(1,2,3)thiadiazole-7-thiocarboxylate;    -   14) Famoxadone, corresponding to        5-methyl-5-(4-phenoxyphenyl)-3-(phenylamino)oxazolidin-2,4-dione;    -   15) Fenamidone, corresponding to        4-methyl-4-phenyl-1-(phenylamino)-2-methylthio-imidazolidin-5-one;    -   16) Cyazofamide, corresponding to        2-cyano-4-chloro-′5-(4-methylphenyl)-1-(N,N-dimethylaminosulfamoyl)-imidazole;    -   17) Fluazinam, corresponding to        3-chloro-N-(3-chloro-5-trifluoromethyl-2-pyridyl)-α,α,α-trifluoro-2,6-dinitro-p-toluidine;    -   18) Dimethomorph, corresponding to        (E,Z)-4-[3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloyl]-morpholine;        or    -   Flumorph (SYP-L190) corresponding to        (E,Z)-4-[3-(4-fluorophenyl)-3-(3,4-dimethoxyphenyl)-acryloyl]morpholine;    -   19) Flumetover, corresponding to        N,N-diethyl-[4-trifluoromethyl-6-(3,4-dimethoxyphenyl)]benzamide    -   20) Chlorothalonil, corresponding to        1,3-dicyano-2,4,5,6-tetrachlorobenzene;    -   21) Thiram, corresponding to        bis-(dimethyl-thiocarbamoyl)disulfide(polymer);    -   22) Propineb, corresponding to the zinc salt of        propylenebis(dithiocarbamate)(polymer);    -   23) Mancozeb, corresponding to the manganese and zinc salt of        ethylenebis(dithiocarbamate)(polymer);    -   24) Maneb, corresponding to the manganese salt of        ethylenebis(dithiocarbamate)(polymer);    -   25) Zineb, corresponding to the zinc salt of        ethylenebis(dithiocarbamate)(polymer);    -   26) Dichlofluanide, corresponding to        N-dichloro-fluoromethylthio-N′,N′-dimethyl-N-phenyl-sulfamide;    -   27) Tolylfluanide, corresponding to        N-dichlorofluoro-methylthio-N′-N′-dimethyl-N-p-tolylsulfamide;    -   28) Captan, corresponding to        N-(trichloromethylthio)cyclohex-4-ene-1,2-carboximide;    -   29) Folpet, corresponding to N-(trichloromethylthio)phthalimide;    -   30) Dithianon, corresponding to        5,10-dihydro-5,10-dioxonaphtho-[2,3-b]-1,4-dithiine-2,3-dicarbonitrile;    -   31) Etridiazole, corresponding to        ethyl-3-trichloromethyl-1,2,4-thiadiazolyl ether;    -   32) Hymexazol, corresponding to 5-methylisoxazol-3-ol;    -   33) Protiocarb, corresponding to        S-ethyl-(3-dimethylaminopropyl)thiocarbamate;    -   34) Propamocarb, corresponding to propyl        (3-dimethylamino)propylcarbamate;    -   35) a copper (I) or copper (II) salt, such as copper        oxychloride, copper hydroxide, or the copper sulfate;    -   36) Mepanipyrim, corresponding to        N-(4-methyl-6-prop-1-inylpyrimidin-2-yl)aniline;    -   37) Pirymethanil, corresponding to        N-(4,6-dimethylpyrimidin-2-yl)aniline;    -   38) Cyprodinil, corresponding to        N-(4-methyl-6-cyclopropylpyrimidin-2-yl)aniline;    -   39) R-3-aminobutanoic acid or RS-3-aminobutanoic acid;    -   40) Zoxamide, corresponding to        3,5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-p-toluamide;    -   41) salicylic acid or its derivatives, such as copper salts of        salicylic acid or of acetyl salicylic acid;    -   42) Trifloxystrobin, corresponding to methyl        (E,E)-methoxyimino-{2-[1-(3-trifluoromethylphenyl)-ethylideneaminooxymethyl]phenyl}acetate;    -   43) Pyraclostrobin, corresponding to methyl        N-(2-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxymethyl}phenyl)-N-methoxy        carbamate;    -   44) Picoxystrobin, corresponding to methyl        (E)-2-{2-[6-(trifluoromethyl)pyridin-2-yloxymethyl]-phenyl}-3-methoxyacrylate;    -   45) Ethaboxam, corresponding to        N-(α-cyano-2-thenyl)-4-ethyl-2-(ethylamino)-5-thiazolecarboxamide.

The phosphorous acid salt A) is preferably a sodium, potassium;magnesium, manganese or zinc salt.

In the spirit of the present invention, component A) can be a singlesalt of an alkaline or alkaline-earth metal, Mn or Zn of phosphorousacid or a mix of said salts in any proportion.

Still in the spirit of the present invention, the salts of an alkalineor alkaline-earth metal, Mn or Zn of phosphorous acid, can be mono- ordi-basic, or a mix of the same in any proportion.

In particular, component B) is preferably selected from IR5885, IR6141,copper (I) and copper (II) salts (such as copper oxychloride, copperhydroxide, tribasic copper sulfate), dithiocarbamates (such as, forexample, mancozeb, zineb, propineb), folpet.

Even more preferably, component B) is selected from IR5885, IR6141,copper oxychloride and mancozeb.

Preferred fungicidal compositions, according to the present invention,consist of mixtures comprising A) a salt of an alkaline oralkaline-earth metal, Mn or Zn of phosphorous acid, and B) a secondfungicide selected from IR5885 or IR6141, or salts of copper (I) orcopper (II).

Preferred fungicidal compositions according to the present inventionconsist of mixtures comprising A) a salt of an alkaline oralkaline-earth metal, Mn or Zn of phosphorous acid, and B) twoadditional fungicides selected from the following couples: IR5885 andMancozeb, or IR6141 and Mancozeb, or IR5885 and IR6141, or IR5885 andCymoxanil, or IR5885 and copper (I) salts, or IR5885 and copper (II)salts, or IR6141 and copper (I) salts, or IR6141 and copper (II) salts.

Compound (1) is described in “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 148.

Compounds (2) are described in Italian patent application No.MI98A002583.

Compound (3) is described in “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 32.

Compound (4) is described in the patent application WO 98 26654 A2.

Compound (5) is described in the English patent GB 1,500,581.

Compound (6) is described in the patent application WO 96 01559 A1.

Compound (7) is described in the English patent GB 2,058,059.

Compound (8) is described in “Phytopatological News” (1978), Vol. 9,page 142.

Compounds (9) are described in patent applications EP 550,788 and EP775696, respectively.

Compound (10) is described in European patent application EP 382,375.

Compound (11) is described in European patent application EP 253,213.

Compound (12), corresponding to the experimental monogram SSF-126, isdescribed in the U.S. Pat. No. 5,185,242.

Compound (13), is described in the U.S. Pat. No. 4,931,581.

Compound (14) is described in “Brighton Crop Protection Conference—Pestsand Diseases” 1996, Congress Acta.

Compound (15) is described in European patent application EP 629,616.

Compound (16), also called IKF916, is described in European patentapplication EP 705,823.

Compound (17) is described in European patent application EP 31,257.

Compounds (18) are described in European patent application EP 219,756and in “Brighton Crop Protection Conference—Pests and Diseases” 2000,Congress Acta, respectively.

Compound (19) is described in European patent applications EP 360,701and EP 611,232.

Compound (20) is described in “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 120.

Compound (21) is described in “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 534.

Compound (22) is described in “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 469.

Compound (23) is described in “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 339.

Compound (24) is described in. “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 340.

Compound (25) is described in “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 569.

Compound (26) is described in “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 175.

Compound (27) is described in “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 537.

Compound (28) is described in “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 87.

Compound (29) is described in “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 599.

Compound (30) is described in “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 225.

Compound (31) is described in “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 252.

Compound (32) is described in “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 314.

Compound (33) is described in “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 473.

Compound (34) is described in “The Pesticide Manual”, 1983, VII^(th)edition, British Crop Protection Council Ed., page 471.

Compounds (35) are easily found on the market.

Compound (38) is described in the patent application WO 95 15684.

Compounds (39) are described in European patent application EP 753,258.

Compound (40) is described in “Brighton Crop Protection Conference—Pestsand Diseases” 1998, Congress Acta.

Compounds (41) are commercial products and their copper salts aredescribed in Italian patent application No. MI 2001A002430.

Compound (42) is described in “Brighton Crop Protection Conference—Pestsand Diseases” 1998, Congress Acta.

Compounds (43) and (44) are described in “Brighton Crop ProtectionConference—Pests and Diseases” 2000, Congress Acta.

Compound (45) is described in European patent application No. EP 639574.

The fungicidal compositions comprising salts of an alkaline oralkaline-earth metal, Mn or Zn of phosphorous acid, with at least one ofthe compounds (1)-(41), object of the present invention, have a highfungicidal activity with respect to numerous fungal species.

A further object of the present invention relates to the use ofcompositions comprising salts of an alkaline or alkaline-earth metal, Mnor Zn of phosphorous acid, with at least one of the compounds (1)-(45),as fungicides.

Examples of pathogens controlled by said compositions, as well asexamples of application crops, are listed hereunder for illustrativepurposes only and with no limitative intention:

-   Plasmopara viticola (vines);-   Phytophthora infestans (tomatoes, potatoes);-   Phytophthora nicotianae (tobacco, ornamental plants);-   Phytophthora palmivora (cacao);-   Phytophthora cinnamomi (pineapples, citrus fruits);-   Phytophthora capsici (peppers, tomatoes, cucurbitaceae);-   Phytophthora cryptogea (tomatoes, thorn-bushes, ornamental plants);-   Phytophthora megasperma (ornamental plants);-   Phytophthora citri (citrus fruits);-   Peronospora tabacina (tobacco);-   Pseudoperonospora cubensis (cabbages, cucurbitaceae);-   Pseudoperonospora humili (hops);-   Bremia (salads).

The compositions object of the present invention are capable of exertinga considerable fungicidal activity, allowing preventive, protective,prophylactic, systemic, curative and eradicating treatment to beeffected.

The compositions, object of the present invention, can be used indifferent amounts, depending on the crop, pathogen, environmentalconditions and formulation adopted.

In general, the fungicidal compositions according to the presentinvention envisage the following application dosages per hectare:

-   -   1000-4000 g of phosphorous acid salt;    -   5-3500 g for each fungicide from 1) to 41), present in the        composition.

The application of the compositions, object of the present invention,can be effected on any part of the plant, for example on the leaves,stems, branches and roots, or on the seeds themselves before sowing, oron the ground in which the plant grows.

The compositions, object of the present invention, are used inagronomical practice under various forms, such as, for example: drypowders, wettable powders, emulsifying concentrates, micro-emulsions,pastes, granules, solutions, suspensions, etc. The choice of the type ofcomposition depends on the specific use.

The compositions are prepared in the known manner, for example bydiluting or dissolving the active substance with a solvent medium and/ora solid diluent, possibly in the presence of surface-active agents.

Solid diluents or carriers which can be used are: silica, kaolin,bentonite, talc, infusorial earth, dolomite, calcium carbonate,magnesia, chalk, clays, synthetic silicates, attapulgite, sepiolite.

Various solvents can be used as liquid diluents in addition to water,for example aromatic solvents (xylols, or mixtures of alkyl benzenes),paraffins (oil fractions), alcohols (methanol, propanol, butanol,octanol, glycerin), amines, amides (N,N-dimethyl formamide, N-methylpyrrolidone), ketones (cyclohexanone, acetone, acetophenone, isophorone,ethyl amyl ketone), fatty acids (for example vegetable oils, such asrape oil, sun flower oil), esters (isobutyl acetate, methyl esters offatty acids obtained, for example, from the transesterification ofvegetable oils).

Sodium, calcium, triethanol amine salts, or triethyl amine of alkylsulphonates, alkyl aryl sulphonates, polyethoxylated alkyl phenols,fatty acids condensed with ethylene oxide, polyoxyethylated fatty acids,polyoxyethylated esters of sorbitole, lignin sulfonates, can be used assurface-active agents.

The compositions can also contain special additives for particularpurposes, such as, for example, adhesion agents, such as gum Arabic,polyvinyl alcohol, polyvinyl pyrrolidone.

In the fungicidal compositions, object of the present invention, theconcentration of active substances ranges from 0.1 to 98%, preferablyfrom 0.5 to 90%.

Other compatible active principles can be added, if desired, to thecompositions, object of the present invention, such as, for example,phyto-regulators, antibiotics, herbicides, insecticides, fertilizers.The following examples are provided for purely illustrative andnon-limiting purposes of the present invention. The potassium phosphite(K₂HPO₃+KH₂PO₃) solution utilized in the following examples 1-4 isobtained by neutralizing at pH 6.6 with potassium hydroxide a solutionof 500 g/l of phosphorous acid in water.

EXAMPLE 1

Determination of the fungicidal efficacy against downy mildew(Plasmopara viticola) of compositions object of the present invention,in preventive application to vine leaves.

The efficacy field tests for the control of Plasmopara viticola arecarried out using an experimental random block scheme which envisages 4repetitions and 6-8 plants per repetition.

The vines, Barbera variety, are treated by spraying both sides of theleaves with a composition based on potassium phosphite (K₂HPO₃+KH₂PO₃)in water solution in an extemporaneous mix with the compound IR6141(compound nr. 4); or in an extemporaneous mix with the compound IR5885(compound nr.2), suitably formulated as a wettable powder 25W; or in anextemporaneous mix with a composition based on the compound IR5885 andcopper oxychloride, formulated as a wettable powder.

The tests are carried out by treating the mixtures of a solution ofpotassium phosphite with IR 6141 at a fixed cadence every 7 days, andthe mixtures of said solution of potassium phosphite with IR 5885, or IR5885 and copper oxychloride, at a fixed cadence every 10 days.

The measurements, effected when the presence of the pathogen agent isrevealed on the non-treated blank lot, are made on both the leaves andbunches.

The leaf measurement is effected by counting 100 leaves of vine per lot(for a total of 400 leaves) and determining the percentage of leafsurface affected by the disease.

The bunch measurement is effected by analyzing all of them andconsidering the percentage of damaged surface.

The data relating to field tests carried out in Piemonte and Emilia withcompositions based on potassium salts of phosphorous acid in anextemporaneous mix with the compound IR5885 (compound nr. 2); or in anextemporaneous mix with the compound IR6141 (compound nr. 4); or in anextemporaneous mix with a composition based on the compound IR5885 andcopper oxychloride (example of compound nr. 35) in comparison with thesame in a mix with Aluminum Fosetyl, are shown in tables 1-2. TABLE 1Average of 4 tests carried out on vines in Italy, during theexperimental season 2002 % disease % disease Dosages active controlcontrol principle (g/hl) leaves bunch IR6141 + potassium phosphite 10 +120 95 93 IR6141 + aluminum Fosetyl 10 + 120 92 90 Non-treated blank (*)78 45(*) % disease index

TABLE 2 Average of 5 tests carried out on vines in Italy, during theexperimental season 2002 % disease % disease Dosages active controlcontrol principle (g/hl) leaves bunch IR5885 + potassium phosphite 12 +120 94 97 IR5885 + aluminum Fosetyl 12 + 120 92 94 IR5885 + copperoxychloride + 12 + 90 + 120 99 99 potassium phosphite IR5885 + copperoxychloride + 12 + 90 + 120 93 96 aluminum Fosetyl Non-treated blank (*)84 65(*) % disease index

EXAMPLE 2

Determination of the fungicidal efficacy against downy mildew(Plasmopara viticola) in preventive application to vine leaves.

Analogously to what is described in example 1, field efficacy tests areeffected for the control of Plasmopara viticola on vines.

The vine plants, Barbera variety, are sprayed with a composition basedon potassium phosphite (K₂HPO₃+KH₂PO₃) in water solution in anextemporary mix with copper oxychloride (example of compound nr. 35),formulated with a wettable powder 50WP.

Tests are carried out by treatment at a fixed cadence every 7 days.

The data relating to field tests carried out in Piemonte and Emilia withcompositions-based on potassium salts of phosphorous acid in anextemporaneous mix with copper oxychloride compared with the analogousmix with Aluminum Fosetyl, are indicated in table 3. TABLE 3 Average of2 tests carried out on vines in Italy, during the experimental season2002 Dosages active % disease % disease con- principle (g/hl) controlleaves trol bunch Copper oxychloride + 80 + 120 81 95 potassiumphosphite Copper oxychloride + 80 + 120 58 73 aluminum FosetylNon-treated 45 87 blank (*)(*) % disease index

EXAMPLE 3

Determination of the fungicidal efficacy against potato downy mildew(Phytophthora infestans) of compositions object of the presentinvention, in preventive application to the leaves of potato plants.

The efficacy field tests for the control of Phytophthora infestans arecarried out using a random block experimental scheme which envisages 4repetitions and 18-20 plants per repetition.

The potato plants, Miura variety, are treated by spraying both sides ofthe leaves with a composition based on potassium phosphite(K₂HPO₃+KH₂PO₃) in water solution in an extemporaneous mix with a blendof compounds IR6141 (compound nr. 4) and mancozeb (compound nr. 23); orwith a blend of the compounds IR5885 (compound nr. 2) and mancozeb(compound nr. 23). Both blends are suitably formulated as a wettablepowder WP.

The tests are carried out by treating the mixtures of a solution ofpotassium phosphite with IR 6141 at a fixed cadence every 7 days, andthe mixtures of said solution of potassium phosphite with IR 5885, at afixed cadence every 10 days.

The measurements are carried out when the presence of the pathogen agentis revealed on the non-treated blank lot.

The leaf measurement is effected by counting 100 potato leaves per lot(for a total of 400 leaves) and determining the percentage of leafsurface affected by the disease.

The data relating to field tests carried out in Great Britain and Francewith compositions of potassium salts of phosphorous acid in anextemporaneous mix with a composition of compounds IR5885 (compound nr.2) and mancozeb (compound nr. 23); or in an extemporaneous mix with thecomposition of compounds IR6141 (compound nr.4) and mancozeb (compoundnr. 23) compared with analogous blends without potassium salts ofphosphorous acid, are indicated in tables 4 and 5.

The activity of the potassium salt of phosphorous acid alone, allows thepossible synergy of the composition to be determined, by analyzing theresults obtained using the Limpel formula (“Pesticide Science” (1987),vol. 19, pages 309-315):E=x+y−(x*y/100)wherein:

-   -   E is the fungicidal activity expected, in the absence of        synergic effects, from a mix obtained by mixing g. x of compound        X with g. y of compound Y;    -   x is the activity of compound X when used alone with a dosage        of g. x;    -   y is the activity of compound Y when used alone    -   with a dosage of g. y;

As the ratio between the experimental value of the composition (85%) andthe calculated value of E (71%) is higher than 1, a synergic effect isverified. TABLE 4 Average of 3 tests carried out on potato plants inGreat Britain, during the experimental season 2002 Dosages active %disease control principle (g/hl) leaves IR6141 + mancozeb + 80 + 1300 +85 potassium phosphite + 1400 IR6141 + mancozeb 80 + 1300 62 Potassiumphosphite 1400 23 Non-treated 95 blank (*)(*) % disease index

TABLE 5 Average of 4 tests carried out on potato plants in France,during the experimental season 2002 Dosages active % disease controlprinciple (g/hl) leaves IR5885 + mancozeb + 120 + 1200 + 90 potassiumphosphite + 1400 IR5885 + mancozeb 120 + 1200 76 Non-treated 89 blank(*)(*) % disease index

EXAMPLE 4

Determination of the fungicidal efficacy against downy mildew(Plasmopara viticola) in preventive application to vine leaves ingreenhouse.

Leaves of vine plants, cv. Dolcetto, grown up in pots in conditionedenvironment at 25° C. and 60% relative humidity, were sprayed on bothsides with hydroacetonic solutions (20% of acetone by volume) of thecompounds under testing, the potassium phosphite (K₂HPO₃+KH₂PO₃) aqueoussolutions and the mixtures of both components.

Seven days after the treatments, the leaves of treated plants anduntreated controls were sprayed on the lower surface with aqueoussuspension of Plasmopara viticola conidia (200.000 conidia/ml); afterbeeing kept for 24 h at 21° C. in environment moist at saturation, theplants were transfered to other conditioned environment at 70% relativehumidity and 21° C. for 7 days.

After this period the degree of infection was evaluated and the activityof the compounds tested was expressed as % of disease control incomparison to the untreated controls: 100=healty plant; 0=completelyinfected plant.

In tables 6-20 are reported the results obtained for the compoundstested alone and in mixture with potassium phosphite at the indicateddosages. When the % disease control value found is higher than the valueexpected applying the Limpel formula (see Example 3), a synergic effectis verified. TABLE 6 Activity of potassium phosphite + cymoxanil(compound 1) against Plasmopara viticola on vine leaves. Dosages active% Disease Control: Compound tested principle (ppm) found expectedcymoxanil 30 59 — potassium phosphite 60 35 — cymoxanil + potassiumphosphite 30 + 60 80 73.35

TABLE 7 Activity of potassium phosphite + metalaxyl (compound 5) againstPlasmopara viticola on vine leaves. Dosages active % Disease Control:Compound tested principle (ppm) found expected metalaxyl 0.20 45 —potassium phosphite 60 35 — metalaxyl + potassium phosphite 0.20 + 60 7664.25

TABLE 8 Activity of potassium phosphite + mefenoxam (compound 6) againstPlasmopara viticola on vine leaves. Dosages active % Disease Control:Compound tested principle (ppm) found expected mefenoxam 0.10 48 —potassium phosphite 60 35 — mefenoxam + potassium phosphite 0.10 + 60 7766.20

TABLE 9 Activity of potassium phosphite + iprovalicarb againstPlasmopara viticola on vine leaves. Dosages active % Disease Control:Compound tested principle (ppm) found expected iprovalicarb 0.45 50 —potassium phosphite 60 35 — iprovalicarb + potassium phosphite 0.45 + 6084 67.50

TABLE 10 Activity of potassium phosphite + benthia- valicarb againstPlasmopara viticola on vine leaves. Dosages active % Disease Control:Compound tested principle (ppm) found expected benthiavalicarb 0.25 47 —potassium phosphite 60 35 — benthiavalicarb + potassium 0.25 + 60 8065.55 phosphite

TABLE 11 Activity of potassium phosphite + azoxystrobin (compound 10)against Plasmopara viticola on vine leaves. Dosages active % DiseaseControl: Compound tested principle (ppm) found expected azoxystrobin0.11 69 — potassium phosphite   60 35 — azoxystrobin + 0.11 + 60 8579.85 potassium phosphite

TABLE 12 Activity of potassium phosphite + famoxadone (compound 14)against Plasmopara viticola on vine leaves. Dosages active % DiseaseControl: Compound tested principle (ppm) found expected famoxadone 0.4556 — potassium phosphite   60 35 — famoxadone + 0.45 + 60 81 71.40potassium phosphite

TABLE 13 Activity of potassium phosphite + fenamidone (compound 15)against Plasmopara viticola on vine leaves. Dosages active % DiseaseControl: Compound tested principle (ppm) found expected fenamidone 10 60— potassium phosphite 60 35 — fenamidone + 10 + 60 85 74.00 potassiumphosphite

TABLE 14 Activity of potassium phosphite + cyazofamide (compound 16)against Plasmopara viticola on vine leaves. Dosages active % DiseaseControl: Compound tested principle (ppm) found expected cyazofamide 1568 — potassium phosphite 60 35 — cyazofamide + 15 + 60 87 79.20potassium phosphite

TABLE 15 Activity of potassium phosphite + dimethomorph (compound 18)against Plasmopara viticola on vine leaves. Dosages active % DiseaseControl: Compound tested principle (ppm) found expected dimethomorph0.45 73 — potassium phosphite   60 35 — dimethomorph + 0.45 + 60 9182.45 potassium phosphite

TABLE 16 Activity of potassium phosphite + chlorothalonil (compound 20)against Plasmopara viticola on vine leaves. Dosages active % DiseaseControl: Compound tested principle (ppm) found expected chlorothalonil7.5 46 — potassium phosphite  60 35 — chlorothalonil + 7.5 + 60 72 64.90potassium phosphite

TABLE 17 Activity of potassium phosphite + zoxamide (compound 40)against Plasmopara viticola on vine leaves. Dosages active % DiseaseControl: Compound tested principle (ppm) found expected zoxamide 0.45 54— potassium phosphite   60 35 — zoxamide + 0.45 + 60 76 70.10 potassiumphosphite

TABLE 18 Activity of potassium phosphite + oxadixyl (compound 7) againstPlasmopara viticola on vine leaves. Dosages active % Disease Control:Compound tested principle (ppm) found expected oxadixyl 0.20 49 —potassium phosphite   60 35 — oxadixyl + 0.20 + 60 74 66.85 potassiumphosphite

TABLE 19 Activity of potassium phosphite + ofurace (compound 8) againstPlasmopara viticola on vine leaves. Dosages active % Disease Control:Compound tested principle (ppm) found expected ofurace 0.20 53 —potassium phosphite   60 35 — ofurace + 0.20 + 60 79 69.45 potassiumphosphite

TABLE 20 Activity of potassium phosphite + fluazinam (compound 17)against Plasmopara viticola on vine leaves. Dosages active % DiseaseControl: Compound tested principle (ppm) found expected fluazinam 20 48— potassium phosphite 60 35 — fiuazinam + 20 + 60 71 66.20 potassiumphoshite

1. Fungicidal compositions characterized in that they comprise A) atleast one salt of an alkaline or alkaline-earth metal, Mn or Zn ofphosphorous acid and B) at least a second fungicidal component.
 2. Thefungicidal compositions according to claim 1, characterized in that thefungicidal component B) is selected from: 1) Cymoxanil, corresponding to1-(2-cyano-2-methoxy imino-acetyl)-3-ethyl urea; 2) IR5885, a dipepticcomponent corresponding to diastereoisomeric mixtures ofmethyl[S-(R,S)]-[3-(N-isopropoxycarbonylvalinyl)-amino]-3-(4-chloro-phenyl)propanoatein any proportion, or to one of the two diastereoisomeric forms S—R orS—S, considered singly; 3) Benalaxyl, corresponding to methyl N-(phenylacetyl)-N-2,6-xylyl-RS-alaninate; 4) IR 6141, corresponding to methylN-(phenyl acetyl)-N-2,6-xylyl-R-alaninate; 5) Metalaxyl, correspondingto methyl N-(2-methoxy acetyl)-N-2,6-xylyl-RS-alaninate; 6) Mefenoxam,corresponding to methyl N-(2-methoxy acetyl)-N-2,6-xylyl-R-alaninate; 7)Oxadixyl, corresponding to2-methoxy-N-(2-oxo-1,3-oxazolidin-3-yl)aceto-2′,6′-xylidide; 8) Ofurace,corresponding toDL-3-[N-chloroacetyl-N-(2,6-xylyl)-amino]-γ-butyrolactone; 9)Iprovalicarb, corresponding toO-(1-methyl-ethyl)-N-[2-methyl-1-[[[1-(4-methyl-phenyl)-ethyl]amino]carbonyl]propyl]carbamate,or Benthiavalicarb-isopropyl corresponding toO-isopropyl[(S)-1-{[(1R)-1-(6-fluoro-1,3-benzothiazol-2-yl)ethyl]-carbamoyl-2-methylpropyl]carbamate;10) Azoxystrobin, corresponding tomethyl(E)-2-[2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]phenyl-3-methoxyacrylate; 11) Kresoxym-methyl corresponding tomethyl(E)-methoxyimino-α-[(o-tolyloxy)-o-tolyl]-acetate; 12)Metominofen, corresponding toN-methyl-(E)-methoxyimino-(2-phenoxyphenyl)acetamide; 13) Acibenzolar,corresponding to methyl benzothiadiazole-7-thiocarboxylate; 14)Famoxadone, corresponding to5-methyl-5-(4-phenoxyphenyl)-3-(phenylamino)oxazo-lydin-2,4-dione; 15)Fenamidone, corresponding to4-methyl-4-phenyl-1-(phenylamino)-2-methylthioimidazo-lydin-5-one; 16)Cyazofamide, corresponding to2-cyano-4-chloro-5(4-methylphenyl)-1-(N,N-dimethylaminosulfamoyl)imidazole;17) Fluazinam, corresponding to3-chloro-N-(3-chloro-5-trifluoromethyl-2-pyridyl)-α,α,α-trifluoro-2,6-dinitro-p-toluidine;18) Dimethomorph, corresponding to(E,Z)-4-[3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)-acryloyl]morpholine;or Flumorph (SYP-L190) corresponding to(E,Z)-4-[3-(4-fluorophenyl)-3-(3,4-dimethoxyphenyl)-acryloyl]morpholine;19) Flumetover, corresponding to N,N-diethylamide of4-trifluoromethyl-6-(3,4-dimethoxyphenyl)-benzoic acid; 20)Chlorothalonil, corresponding to 1,3-dicyano-2,4,5,6-tetrachlorobenzene;21) Thiram, corresponding tobis-(dimethyl-thiocarbamoyl)disulfide(polymer); 22) Propineb,corresponding to the zinc salt ofpropylenebis(dithiocarbamate)(polymer); 23) Mancozeb, corresponding tothe manganese and zinc salt of ethylenebis(dithiocarbamate)(polymer);24) Maneb, corresponding to the manganese salt ofethylenebis(dithiocarbamate)(polymer); 25) Zineb, corresponding to thezinc salt of ethylenebis(dithiocarbamate)(polymer); 26) Dichlofluanide,corresponding to N-dichloro-fluoromethylthio-N′,N′-dimethyl-N-phenylsulfamide; 27) Tolylfluanide, corresponding toN-dichloro-fluoro-methylthio-N′-N′-dimethyl-N-p-tolylsulfamide; 28)Captano, corresponding toN-(trichloro-methylthio)cyclohex-4-ene-1,2-carboximide; 29) Folpet,corresponding to N-(trichloro-methylthio)phthalimide; 30) Dithianon,corresponding to5,10-dihydro-5,10-dioxonaphthol-[2,3-b]-1,4-dithi-in-2,3-dicarbo-nitrile;31) Etridiazole, corresponding toethyl-3-trichloromethyl-1,2,4-thiadiazolyl ether; 32) Hymexanol,corresponding to 5-methylisoxazol-3-ole; 33) Protiocarb, correspondingto S-ethyl-(3-dimethylaminopropyl)thiocarbamate; 34) Propamocarb,corresponding to propyl-(3-dimethylaminopropyl)carbamate; 35) A copper(I) or copper (II) salt, such as copper oxychloride, copper hydroxide,or the copper sulfate; 36) Mepanipyrim, corresponding toN-(4-methyl-6-prop-1-inylpyrimidin-2-yl)aniline; 37) Pirymethanil,corresponding to N-(4,6-dimethyl-pyrimidin-2-yl) aniline; 38)Cyprodinil, corresponding toN-(4-methyl-6-cyclopropylpyrimidin-2-yl)aniline; 39) R-3-amino butanoicacid or RS-3-amino butanoic acid; 40) Zoxamide, corresponding to3,5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-p-toluamide; 41)Salicylic acid or its derivatives, such as copper salts of salicylicacid or of acetyl salicylic acid; 42) Trifloxystrobin, corresponding tomethyl(E,E)-methoxyimino-{2-[1-(3-trifluoromethylphenyl)-ethylideneaminooxymethyl]phenyl}acetate;43) Pyraclostrobin, corresponding to methylN-(2-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxymethyl}phenyl)-N-methoxycarbamate: 44) Picoxystrobin, corresponding to methyl(E)-2-{2-[6-(trifuoromethyl)pyridin-2-yloxymethyl]-phenyl}-3-methoxyacrylate;45) Ethaboxan, corresponding toN-(α-cyano-2-thenyl)-4-ethyl-2-(ethylamino)-5-thiazolecarboxamide. 3.The fungicidal compositions according to claim 1, characterized in thatthe phosphorous acid salt A) is selected from sodium, potassium,magnesium, manganese and zinc salt.
 4. The fungicidal compositionsaccording to claim 1, characterized in that component A) is a singlesalt or a mix of salts of phosphorous acid in any proportion.
 5. Thefungicidal compositions according to claim 1, characterized in thatcomponent A) is a mono- or di-basic salt, or a mixture of the same inany proportion.
 6. The fungicidal compositions according to claim 2,characterized in that component B) is selected from IR5885, IR6141,copper (I) and copper (II) salts (such as copper oxychloride, copperhydroxide, tribasic copper sulfate), dithio-carbamates (such as, forexample, mancozeb, zineb, propineb), folpet.
 7. The fungicidalcompositions according to claim 2, characterized in that component B) isselected from IR5885, IR6141, copper oxychloride and mancozeb.
 8. Thefungicidal compositions according to claim 2, characterized in that theyconsist of mixtures comprising A) a salt of an alkaline oralkaline-earth metal, Mn or Zn of phosphorous acid, and B) a secondfungicide selected from IR5885 or IR6141, or salts of copper (I) orcopper (II).
 9. The fungicidal compositions according to claim 2,characterized in that they consist of mixtures comprising A) a salt ofan alkaline or alkaline-earth metal, Mn or Zn of phosphorous acid, andB) two additional fungicides selected from IR5885 and Mancozeb, orIR6141 and Mancozeb, or IR5885 and IR6141, or IR5885 and Cymoxanil, orIR5885 and copper (I) salts, or IR5885 and copper (II) salts, or IR6141and copper (I) salts, or IR6141 and copper (II) salts.
 10. Thefungicidal compositions according to any of the previous claims,characterized in that the components are present in the followingapplication dosages per hectare: 1000-4000 g of phosphorous acid salt;5-3500 g for each fungicide from 1) to 41), present in the composition.11. The fungicidal compositions according to claim 1, characterized inthat they are formulated as dry powders, wettable powders, emulsifyingconcentrates, micro-emulsions, pastes, granules, solutions, suspensions,etc.
 12. The fungicidal compositions according to claim 1 characterizedin that they comprise other compatible active principles such asphyto-regulators, antibiotics, herbicides, insecticides, fertilizers.13. The fungicidal compositions according to claim 1, characterized inthat the concentration of active substances ranges from 0.1 to 98%,preferably from 0.5 to 90%.
 14. Use of the compositions according toclaim 1 as fungicides in the agronomical field.
 15. Use according toclaim 1, for the control of phytopathogen fungi such as Plasmoparaviticola (vines); Phytophthora infestans (tomatoes, potatoes);Phytophthora nicotianae (tobacco, ornamental plants); Phytophthorapalmivora (cacao); Phytophthora cinnamomi (pineapples, citrus fruits);Phytophthora capsici (peppers, tomatoes, cucurbitaceae); Phytophthoracryptogea (tomatoes, thorn-bushes, ornamental plants); Phytophthoramegasperma (ornamental plants); Phytophthora citri (citrus fruits);Peronospora tabacina (tobacco); Pseudoperonospora cubensis (cabbages,cucurbitaceae); Pseudoperonospora humili (hops); Bremia (salads). 16.Method for controlling phytopathogen fungi in crops of agricultural andhorticultural interest, using the compositions according to claim
 1. 17.The method according to claim 16, characterized in that the applicationis effected on any part of the plant by application on the leaves,stems, branches and roots, or on the seeds themselves before sowing, oron the ground in which the plant grows.